The potential （E）-dependent vibrational behavior of a saturated CO adlayer on Au-core Pd-shell nanoparticle film electrodes was investigated over a wide potential range, in acidic, neutral, and basic solutions, usin...The potential （E）-dependent vibrational behavior of a saturated CO adlayer on Au-core Pd-shell nanoparticle film electrodes was investigated over a wide potential range, in acidic, neutral, and basic solutions, using in situ surface-enhanced Raman spectroscopy （SERS）. Over the whole of the examined potential region （-1.5 to 0.55 V vs. NHE）, the peak frequencies of both the C-OM and the Pd-COM band （here, M denotes the multiply-bonded configuration） displayed three distinct linear regions： dvc oM/dE decreased from -185-207 （from -1.5 to -1.2 V） to -83-84 cm-1/V （-1.2 to -0.15 V）, and then to 43 cm-1/V （-0.2 to 0.55 V）; on the other hand, dvpd coM/dE changed from -10 to -8 cm I/V （from -1.5 to -1.2 V） to ^-31 to -30 cm-1/V （-1.2 to -0.15 V）, and then to -15 cm-1/V （-0.2 to 0.55 V）. The simultaneously recorded cyclic voltammograms revealed that at E 〈 -1.2 V, a hydro- gen evolution reaction （HER） occurred. With the help of periodic density functional theory calcula- tions using two different （2 × 2）-3CO slab models with Pd（111）, the unusually high dvc-oM/dE and the small dVPd-CoM/dE in the HER region were explained as being due to the conversion of COad from bridge to hollow sites, which was induced by the co-adsorbed hydrogen atoms formed from dissociated water at negative potentials.展开更多
基金supported by the National Natural Science Foundation of China(21473175)the National Instrumentation Program(2011YQ03012416)the National Basic Reserarch Program of China(973 Program,2015CB932301)
文摘The potential （E）-dependent vibrational behavior of a saturated CO adlayer on Au-core Pd-shell nanoparticle film electrodes was investigated over a wide potential range, in acidic, neutral, and basic solutions, using in situ surface-enhanced Raman spectroscopy （SERS）. Over the whole of the examined potential region （-1.5 to 0.55 V vs. NHE）, the peak frequencies of both the C-OM and the Pd-COM band （here, M denotes the multiply-bonded configuration） displayed three distinct linear regions： dvc oM/dE decreased from -185-207 （from -1.5 to -1.2 V） to -83-84 cm-1/V （-1.2 to -0.15 V）, and then to 43 cm-1/V （-0.2 to 0.55 V）; on the other hand, dvpd coM/dE changed from -10 to -8 cm I/V （from -1.5 to -1.2 V） to ^-31 to -30 cm-1/V （-1.2 to -0.15 V）, and then to -15 cm-1/V （-0.2 to 0.55 V）. The simultaneously recorded cyclic voltammograms revealed that at E 〈 -1.2 V, a hydro- gen evolution reaction （HER） occurred. With the help of periodic density functional theory calcula- tions using two different （2 × 2）-3CO slab models with Pd（111）, the unusually high dvc-oM/dE and the small dVPd-CoM/dE in the HER region were explained as being due to the conversion of COad from bridge to hollow sites, which was induced by the co-adsorbed hydrogen atoms formed from dissociated water at negative potentials.
